U.S. patent application number 17/378904 was filed with the patent office on 2022-04-28 for water-based polyurethane resin and manufacturing method thereof.
The applicant listed for this patent is NAN YA PLASTICS CORPORATION. Invention is credited to SEN-HUANG HSU, TE-CHAO LIAO, CHIA-LUNG TSAI.
Application Number | 20220127406 17/378904 |
Document ID | / |
Family ID | 1000005783279 |
Filed Date | 2022-04-28 |
United States Patent
Application |
20220127406 |
Kind Code |
A1 |
LIAO; TE-CHAO ; et
al. |
April 28, 2022 |
WATER-BASED POLYURETHANE RESIN AND MANUFACTURING METHOD THEREOF
Abstract
A water-based polyurethane resin and a method for manufacturing
the same are provided. The method for manufacturing the water-based
polyurethane includes: a preparation step of a prepolymer, a
dilution step of the prepolymer, a water dispersion and chain
extension step, and an acrylic synthesis step. The method further
includes mixing polyol and polyisocyanate to obtain a prepolymer,
and diluting the prepolymer by adding acrylic monomer in the
prepolymer. In the water-based polyurethane resin, at least one of
the polyhydric alcohol, polyisocyanate, and the acrylic monomer
includes a compound with a cyclic structure.
Inventors: |
LIAO; TE-CHAO; (TAIPEI,
TW) ; HSU; SEN-HUANG; (TAIPEI, TW) ; TSAI;
CHIA-LUNG; (TAIPEI, TW) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
NAN YA PLASTICS CORPORATION |
TAIPEI |
|
TW |
|
|
Family ID: |
1000005783279 |
Appl. No.: |
17/378904 |
Filed: |
July 19, 2021 |
Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C08G 18/673 20130101;
C08G 18/0866 20130101; C08G 18/088 20130101; C08G 18/4241 20130101;
C08G 18/10 20130101 |
International
Class: |
C08G 18/10 20060101
C08G018/10; C08G 18/08 20060101 C08G018/08; C08G 18/42 20060101
C08G018/42; C08G 18/67 20060101 C08G018/67 |
Foreign Application Data
Date |
Code |
Application Number |
Oct 26, 2020 |
TW |
109137020 |
Claims
1. A method for manufacturing a water-based polyurethane resin,
comprising: (1) a preparation step of a prepolymer:
vacuum-dehydrating 15 to 25 wt % of a polyol and adding the
vacuum-dehydrated polyol into a reactor, and adding 5 to 12 wt % of
a polyisocyanate into the reactor when an oil bath temperature
reaches 70.degree. C. to 80.degree. C. to carry out a synthetic
reaction so as to obtain the prepolymer; (2) a dilution step of the
prepolymer: adding 10 to 30 wt % of an acrylic monomer to reduce
the viscosity of the prepolymer and maintaining a reaction
temperature at 85.degree. C. to 90.degree. C. for 2 to 3 hours,
until an NCO content (NCO %) of the prepolymer reaches a target
value, and subsequently adding 1.8 to 3.7 wt % of sulfonate
hydrophilic agent to continue the reaction for 25 to 40 minutes so
as to obtain a polymer; (3) a water dispersion and chain extension
step: cooling the polymer obtained from the step (2) to room
temperature and adding 35 to 55 wt % of deionized water to the
polymer under a high-speed shearing force that is generated at a
rotational speed of 500 rpm, and subsequently adding 0.1 to 0.5 wt
% of a chain extender to carry out a chain extension reaction for
30 minutes so as to obtain a water-based polyurethane dispersion;
and (4) an acrylic synthesis step: mixing the water-based
polyurethane dispersion obtained from the step (3) with 0.3 to 1.0
wt % of an emulsifier to form an emulsion, raising the reaction
temperature to 50.degree. C. to 70.degree. C. after stirring evenly
and then dropwise adding 0.01 to 0.10 wt % of an initiator,
carrying out an acrylic polymerization reaction at 75.degree. C. to
85.degree. C. for 1 to 3 hours, and adding 0.01 to 0.08 wt % of a
reducing agent after reducing the reaction temperature to
50.degree. C. to 70.degree. C. so as to obtain the water-based
polyurethane resin; wherein at least one of the polyol, the
polyisocyanate and the acrylic monomer includes a cyclic structure
compound.
2. The method according to claim 1, wherein all of the polyol, the
polyisocyanate and the acrylic monomer include a cyclic structure
compound.
3. The method according to claim 1, wherein the polyol is selected
from a group consisting of a polyester polyol, a polyether polyol
and a polycarbonate polyol.
4. The method according to claim 3, wherein the polyester polyol is
formed by polymerizing 1,4 cyclohexane dimethanol or tricyclodecane
dimethanol and dibasic acid.
5. The method according to claim 1, wherein the polyisocyanate is
selected from the group consisting of toluene diisocyanate (TDI),
isophorone diisocyanate (IPDI), diphenylmethane diisocyanate (MDI)
and dicyclohexylmethane diisocyanate (H.sub.12MDI).
6. The method according to claim 1, wherein the polyol and the
polyisocyanate are reacted in an NCO/OH equivalent ratio from 1.1
to 2.3.
7. The method according to claim 1, wherein the acrylic monomer is
selected from the group consisting of cyclohexyl methacrylate
(CHMA), isobornyl methacrylate (IBOMA), 2-hydroxyethyl acrylate
(2-HEA), methyl methacrylate (MMA) and ethyl acrylate (EA).
8. The method according to claim 1, wherein, based on a total
weight of the acrylic monomer, the acrylic monomer includes: (a) 50
to 90 wt % of methyl methacrylate; (b) 4 to 9 wt % of ethyl
acrylate2-hydroxyethyl acrylate; (c) 2 to 6 wt % of ethyl acrylate;
(d) 0 to 15 wt % of cyclohexyl methacrylate; and (e) 0 to 20 wt %
of isobornyl methacrylate.
9. The method according to claim 1, wherein the initiator is
selected from the group consisting of hydrogen peroxide, tert-butyl
peroxide, sodium persulfate, potassium persulfate, lithium
persulfate and ammonium persulfate, and the amount of the initiator
is 0.01 to 3 wt % based on a total amount of the acrylic
monomer.
10. A water-based polyurethane resin, formed by the method
according to claim 1, wherein the water-based polyurethane resin
includes a cyclic structure.
Description
CROSS-REFERENCE TO RELATED PATENT APPLICATION
[0001] This application claims the benefit of priority to Taiwan
Patent Application No. 109137020, filed on Oct. 26, 2020. The
entire content of the above identified application is incorporated
herein by reference.
[0002] Some references, which may include patents, patent
applications and various publications, may be cited and discussed
in the description of this disclosure. The citation and/or
discussion of such references is provided merely to clarify the
description of the present disclosure and is not an admission that
any such reference is "prior art" to the disclosure described
herein. All references cited and discussed in this specification
are incorporated herein by reference in their entireties and to the
same extent as if each reference was individually incorporated by
reference.
FIELD OF THE DISCLOSURE
[0003] The present disclosure relates to a water-based polyurethane
resin and a manufacturing method thereof, and more particularly to
a water-based polyurethane resin with cyclic structure and a
manufacturing method thereof.
BACKGROUND OF THE DISCLOSURE
[0004] Polyurethane (PU) resin is widely used in various fields,
such as being used as a synthetic leather material or a surface
treatment agent. In the process of producing polyurethane, a large
amount of organic solvent is required, resulting in a problem that
polyurethane product contains volatile organic compounds (VOCs). In
recent years, with the rise of environmental awareness, water-based
polyurethane has gradually replaced solvent-based polyurethanes,
and is widely used in a variety of applications such as coating
processing, leather processing, adhesives, sealants and plastic
molding. The synthesis method of water-based polyurethane is
reacting polyether or polyester polyol with isocyanate to
synthesize a high-viscosity prepolymer having an NCO functional
group at the end.
[0005] When water-based polyurethane is applied as a synthetic
leather material, for example: leather material for car, in which
the condition is under high temperature (120.degree. C..times.7
days), the physical properties such as heat yellowing resistance
and weathering resistance are negatively affected. In the
conventional art, additives such as light stabilizers, antioxidants
and heat stabilizers are applied to achieve the purpose of
improving the yellowing problem. However, the improvement is still
not very satisfactory.
SUMMARY OF THE DISCLOSURE
[0006] In response to the above-referenced technical inadequacies,
the present disclosure provides a water-based polyurethane resin
including cyclic structure and a manufacturing method thereof.
[0007] In one aspect, the present disclosure provides a method for
manufacturing a water-based polyurethane resin, including: (1) a
preparation step of a prepolymer: vacuum-dehydrating 15 to 25 wt %
of a polyol and adding the vacuum-dehydrated polyol into a reactor,
and adding 5 to 12 wt % of a polyisocyanate into the reactor when
an oil bath temperature reaches 70.degree. C. to 80.degree. C. to
carry out a synthetic reaction so as to obtain the prepolymer; (2)
a dilution step of the prepolymer: adding 10 to 30 wt % of an
acrylic monomer to reduce the viscosity of the prepolymer and
maintaining a reaction temperature at 85.degree. C. to 90.degree.
C. for 2 to 3 hours, until an NCO content (NCO %) of the prepolymer
reaches a target value, and subsequently adding 1.8 to 3.7 wt % of
sulfonate hydrophilic agent to continue the reaction for 25 to 40
minutes so as to obtain a polymer; (3) a water dispersion and chain
extension step: cooling the polymer obtained from the step (2) to
room temperature and adding 35 to 55 wt % of deionized water to the
polymer under a high-speed shearing force that is generated at a
rotational speed of 500 rpm, and subsequently adding 0.1 to 0.5 wt
% of a chain extender to carry out a chain extension reaction for
30 minutes so as to obtain a water-based polyurethane dispersion;
and (4) an acrylic synthesis step: mixing the water-based
polyurethane dispersion obtained from the step (3) with 0.3 to 1.0
wt % of an emulsifier to form an emulsion, raising the reaction
temperature to 50.degree. C. to 70.degree. C. after stirring evenly
and then dropwise adding 0.01 to 0.10 wt % of an initiator,
carrying out an acrylic polymerization reaction at 75.degree. C. to
85.degree. C. for 1 to 3 hours, and adding 0.01 to 0.08 wt % of a
reducing agent after reducing the reaction temperature to
50.degree. C. to 70.degree. C. so as to obtain a water-based
polyurethane resin; in which at least one of the polyol, the
polyisocyanate and the acrylic monomer includes a cyclic structure
compound.
[0008] In another aspect, the present disclosure provides a
water-based polyurethane resin, formed by the method of the present
disclosure, in which the water-based polyurethane resin includes a
cyclic structure.
[0009] Therefore, in the water-based polyurethane resin and the
manufacturing method thereof, by virtue of "at least one of the
polyol, the polyisocyanate and the acrylic monomer includes a
cyclic structure compound", the thermal stability of the resin in
the present disclosure is improved.
[0010] These and other aspects of the present disclosure will
become apparent from the following description of the embodiment
taken in conjunction with the following drawings and their
captions, although variations and modifications therein may be
affected without departing from the spirit and scope of the novel
concepts of the disclosure.
BRIEF DESCRIPTION OF THE DRAWINGS
[0011] The described embodiments may be better understood by
reference to the following description and the accompanying
drawings, in which:
[0012] FIG. 1 is a flowchart of a method for manufacturing a
water-based polyurethane resin of the present disclosure.
DETAILED DESCRIPTION OF THE EXEMPLARY EMBODIMENTS
[0013] The present disclosure is more particularly described in the
following examples that are intended as illustrative only since
numerous modifications and variations therein will be apparent to
those skilled in the art. Like numbers in the drawings indicate
like components throughout the views. As used in the description
herein and throughout the claims that follow, unless the context
clearly dictates otherwise, the meaning of "a", "an", and "the"
includes plural reference, and the meaning of "in" includes "in"
and "on". Titles or subtitles can be used herein for the
convenience of a reader, which shall have no influence on the scope
of the present disclosure.
[0014] The terms used herein generally have their ordinary meanings
in the art. In the case of conflict, the present document,
including any definitions given herein, will prevail. The same
thing can be expressed in more than one way. Alternative language
and synonyms can be used for any term(s) discussed herein, and no
special significance is to be placed upon whether a term is
elaborated or discussed herein. A recital of one or more synonyms
does not exclude the use of other synonyms. The use of examples
anywhere in this specification including examples of any terms is
illustrative only, and in no way limits the scope and meaning of
the present disclosure or of any exemplified term. Likewise, the
present disclosure is not limited to various embodiments given
herein. Numbering terms such as "first", "second" or "third" can be
used to describe various components, signals or the like, which are
for distinguishing one component/signal from another one only, and
are not intended to, nor should be construed to impose any
substantive limitations on the components, signals or the like.
[0015] Referring to FIG. 1, the present disclosure provides a
method for manufacturing a water-based polyurethane resin,
including: S100, a preparation step of a prepolymer; S200, a
dilution step of the prepolymer; S300, a water dispersion and chain
extension step; S400, an acrylic synthesis step. The reactants for
manufacturing a water-based polyurethane resin include polyol,
polyisocyanate and acrylic monomer, and at least one of the
reactants includes a cyclic structure compound. More specifically,
at least one of polyol, polyisocyanate, and acrylic monomer
includes a cyclic structure. The cyclic structure compound refers
to a compound in which atoms of the molecule are arranged in a
cyclical shape, for example, alicyclic compounds or aromatic
hydrocarbons. Preferably, the structure of the acrylic monomer
includes a cyclic structure.
[0016] The preparation step of a prepolymer, S100 includes:
vacuum-dehydrating 15 to 25 wt % of a polyol and adding the
vacuum-dehydrated polyol into a reactor, and adding 5 to 12 wt % of
a polyisocyanate into the reactor when an oil bath temperature
reaches 70.degree. C. to 80.degree. C. to carry out a synthetic
reaction so as to obtain the prepolymer.
[0017] The polyol is selected from the group consisting of
polyester polyols and polyether polyols. That is to say, the polyol
can be the polyester polyol or polyether polyol individually, or in
any combinations of multiple different polyester polyols and
polyether polyols.
[0018] The polyester polyol is obtained by a condensation reaction
between a low molecular weight polyol and a dicarboxylic acid. For
example, a low molecular weight polyol selected from the group
consisting of ethylene glycol, 1,3-propanediol and 1,4-butylene
glycol and an aliphatic dicarboxylic acid selected from the group
consisting of succinic acid, glutaric acid, adipic acid,
heptanedioic acid, suberic acid, azelaic acid, sebacic acid, decane
dicarboxylic acid and cyclohexane dicarboxylic acid are used to
form a condensed polyester polyol.
[0019] Furthermore, the polyol can also be an amide-based polyester
amide polyol such as hexamethylene diamine and isophorone diamine,
which is obtained from a cyclic ester (e.g.,
.epsilon.-caprolactone) and a part of the diol component.
[0020] In addition, polyester polyols can also be polymerized by
1,4-cyclohexane dimethanol or tricyclodecane dimethanol
(TCD-alcohol) and dibasic acid, for example, polycyclohexane
dimethyl ester formed by polymerization of 1,4-cyclohexane
dimethanol and dibasic acid, and polytricyclodecane dimethyl ester
formed by polymerization of tricyclodecane dimethanol (TCD-alcohol)
and dibasic acid, as follows.
##STR00001##
[0021] The polyether polyol is selected from the group consisting
of poly(tetramethylene ether) glycol (PTMG), polypropanediol (PPG)
and polyether polyols whose main chain and side chain(s) are poly
ethylene glycol (PEG) chains.
[0022] The diisocyanate may be aliphatic diisocyanate, alicyclic
diisocyanate or aromatic diisocyanate. Preferably, the diisocyanate
is an alicyclic diisocyanate having a cyclic structure.
[0023] For example, the aliphatic diisocyanate may be selected from
the group consisting of tetramethylene diisocyanate, hexamethylene
diisocyanate, decamethylene diisocyanate and lysine
diisocyanate.
[0024] For example, the alicyclic diisocyanate may be toluene
diisocyanate (TDI), methylene diphenyl diisocyanate (MDI),
isophorone diisocyanate (IPDI), xylylene diisocyanate (XDI),
tetramethylxylene diisocyanate, 4,4'-diisocyanato
dicyclohexylmethane (H.sub.12MDI), or trimethylhexamethylene
diisocyanate (TMDI).
[0025] For example, the aromatic isocyanate may be aromatic
diisocyanate, polyphenylene polymethylene polyisocyanate or crude
tolylene diisocyanate such as 2,4-toluene diisocyanate, 2,6-toluene
diisocyanate, xylene-1,4-diisocyanate, xylene-1,3-diisocyanate,
4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane
diisocyanate, 4,4'-diphenyl ether diisocyanate,
2-nitrodiphenyl-4,4'-diisocyanate,
2,2'-diphenylpropane-4,4'-diisocyanate,
3,3'-dimethyldiphenylmethane-4,4'-diisocyanate,
4,4'-diphenylpropanediisocyanate, m-phenyl diisocyanate, p-phenyl
diisocyanate, naphthalene-1,4-diisocyanate,
naphthalene-1,5-diisocyanate, or
3,3'-dimethoxydiphenyl-4,4'-diisocyanate.
[0026] Preferably, the diisocyanate is isophorone diisocyanate
(IPDI) or 4,4'-diisocyanato dicyclohexylmethane (H.sub.12MDI).
[0027] The dilution step of the prepolymer, step S200 includes:
adding 10 to 30 wt % of an acrylic monomer to reduce the viscosity
of the prepolymer and maintaining a reaction temperature at
85.degree. C. to 90.degree. C. for 2 to 3 hours, until an NCO
content (NCO %) of the prepolymer reaches a target value, and
subsequently adding 1.8 to 3.7 wt % of sulfonate hydrophilic agent
to continue the reaction for 25 to 40 minutes so as to obtain a
polymer.
[0028] The acrylic monomer is selected from the group consisting of
cyclohexyl methacrylate, isobornyl methacrylate, methyl acrylate,
methyl methacrylate, ethyl acrylate, isooctyl acrylate, butyl
acrylate, butyl methacrylate, ethylhexyl acrylate, 2-hydroxyethyl
acrylate, monomethyl maleate, monomethyl itaconate, monomethyl
fumarate, and styrene. Preferably, the acrylic monomer is a mixture
of multiple monomers. More preferably, the acrylic monomer is an
acrylate monomer combined with an acrylic monomer having a cyclic
structure.
[0029] Preferably, the acrylic monomer is selected from the group
consisting of cyclohexyl methacrylate (CHMA), isobornyl
methacrylate (IBOMA), 2-hydroxyethyl acrylate (2-HEA), methyl
methacrylate (MMA) and ethyl acrylate (EA).
[0030] More specifically, 2-hydroxyethyl acrylate, methyl
methacrylate and ethyl acrylate can be used as solvents to omit
acetone used in the conventional art. 2-hydroxyethyl acrylate
(2-HEA) containing hydroxyl groups (--OH) can react with
isocyanate, and methyl methacrylate (MMA) and ethyl acrylate (EA)
can increase the molecular weight of acrylic, which strengths the
mechanical strength and improves the water resistance of
water-based polyurethane.
[0031] In addition, both cyclohexyl methacrylate and isobornyl
methacrylate have a cyclic structure, which can improve the heat
resistance and heat yellowing resistance of resin, the structures
are provided below:
##STR00002##
[0032] Specifically, based on a total weight of the acrylic
monomer, the acrylic monomer of the present disclosure is in a
combination as follows: [0033] (a) 50 to 90 wt % of methyl
methacrylate; [0034] (b) 4 to 9 wt % of ethyl
acrylate2-hydroxyethyl acrylate; [0035] (c) 2 to 6 wt % of ethyl
acrylate; [0036] (d) 0 to 15 wt % of cyclohexyl methacrylate; and
[0037] (e) 0 to 20 wt % of isobornyl methacrylate.
[0038] If the acrylic monomer is a simple acrylic acid, the
composition of the water-based polyurethane must further contain
other components with cyclic structure. Naturally, the cyclohexyl
methacrylate and the isobornyl methacrylate with cyclic structures
can provide more excellent yellowing resistance.
[0039] Preferably, based on a total weight of the acrylic monomer,
the acrylic monomer of the present disclosure is in a combination
as follows: [0040] (a) 50 to 90 wt % of methyl methacrylate; [0041]
(b) 4 to 9 wt % of ethyl acrylate2-hydroxyethyl acrylate; [0042]
(c) 2 to 6 wt % of ethyl acrylate; [0043] (d) 7 to 14 wt % of
cyclohexyl methacrylate; and [0044] (e) 10 to 18 wt % of isobornyl
methacrylate.
[0045] The sulfonate hydrophilic agent is used as a polyurethane
hydrophilic agent and can be used as a polymer emulsifier.
Preferably, the sulfonate hydrophilic agent is sodium
ethylenediaminoethoxyethanesulfonate.
[0046] The term "target value of NCO %" refers to, after isocyanato
groups (--NCO) of polyisocyanate are completely reacted with
hydroxyl groups (--OH) of the polyol in a polyurethane (PU)
reaction, the weight percentage of the remaining isocyanato groups
(--NCO) relative to the weight of the total reactants. The target
value of NCO % satisfies the following formula: (the amount of the
polyisocyanate/the molecular weight of the polyisocyanate-the
amount of the polyol/the molecular weight of the
polyol).times.42.times.2.times.%. In the present embodiment, the
NCO content (NCO %) is determined by using di-n-butylamine
titration before the reaction, i.e., before the preparation step of
adding water and carrying out emulsification.
[0047] If the NCO content of the polyurethane resin is between 50%
and 85% of the theoretical NCO content, the polyurethane resin is
stably dispersed in the aqueous polyurethane dispersion so that
generation of formation gels due to the aggregation of the
polyurethane resin can be avoided. If the polyisocyanate is
excessively consumed in the synthesis of the polyurethane resin and
the NCO content of the polyurethane resin is thus less than 50% of
the target value of NCO %, the polyurethane net structure has a
high degree of crosslinking due to the excessive reaction of
polyurethane and causes failure in the form of a large amount of
polyurethane in the aqueous phase being aggregated into gels. If
the NCO content of the polyurethane resin is greater than 85% of
the target value of NCO %, the synthesized polyurethane lacks in
net structure, and after the aqueous polyurethane is processed into
a film, the film has highly viscous surfaces that may cause
adhesion between the films and result in scrappage.
[0048] The water dispersion and chain extension step, S300
includes: cooling the polymer obtained from S200 to room
temperature and adding 35 to 55 wt % of deionized water to the
polymer under a high-speed shearing force that is generated at a
rotational speed of 500 rpm, and subsequently adding 0.1 to 0.5 wt
% of a chain extender to carry out a chain extension reaction for
about 30 minutes so as to obtain a water-based polyurethane.
[0049] Through adjusting the ratio of the diisocyanate, the polyol
and the deionized water, the foaming characteristics of the
resultant can be improved. The chain extender can be selected from
the group consisting of low molecular weight polyamines having a
(number average) molecular weight less than 500, and etc.
[0050] The acrylic synthesis step S400 includes: mixing the
water-based polyurethane obtained from S300 with 0.3 to 1.0 wt % of
an emulsifier to form an emulsion, raising the reaction temperature
to 50.degree. C. to 70.degree. C. after stirring evenly and then
dropwise adding 0.01 to 0.10 wt % of an initiator, carrying out an
acrylic polymerization reaction at 75.degree. C. to 85.degree. C.
for 1 to 3 hours, and adding 0.01 to 0.08 wt % of a reducing agent
after reducing the reaction temperature to 50.degree. C. to
70.degree. C. so as to obtain a water-based polyurethane resin.
Specifically, the emulsifier may be anionic emulsifiers, nonionic
emulsifiers and reactive emulsifiers. For example, the emulsifier
can be tert-octylphenoxyethyl poly(39)-ethoxyethanol, dodecyloxy
poly(10) ethoxyethanol, nonyl phenoxyethyl-poly(40) ethoxyethanol,
polyethyleneglycol(2000) mono-oleate, hydroxyethylated castor oil,
fluorinated alkyl esters and alkyl oxide, polyethylene oxide (20)
sorbitol monolaurate, sucrose monococoate, bis(2-butyl) phenoxy
poly(20) ethoxyethanol, and hydroxyethyl cellulose polybutyl
acrylate graft copolymer. The emulsifier is a surfactant that can
significantly reduce surface tension. Accordingly, oil and water
phases that are insoluble to each other can be transformed by
stirring into a stable white emulsion which is not easily separated
into layers.
[0051] The anionic emulsifier may be sodium lauryl sulfate (SLS),
sodium dodecyl benzene sulfonate, potassium stearate, sodium
dioctyl sulfosuccinate, sodium dodecyldiphenyloxy disulfonate,
sodium styrene sulfonate, nonylphenoxy poly ethyl (1) ethoxyethyl
sulfate ammonium, sodium dodecyl allyl sulfosuccinate, linseed oil
fatty acid, ethoxylated nonylphenol phosphate sodium, ethoxylated
nonylphenol phosphate ammonium, sodium octoxynol-3-sulfate, sodium
cocoyl sarcosinate, 1-alkoxy-2-sodium hydroxypropyl sulfonate,
sodium alpha-olefin (C14-C16) sulfonate, sulfate of hydroxyl anol,
N-(1,2-dicarboxyethyl)-N-octadecylsulfonylsuccinamate tetrasodium,
N-octadecylsulfonylsuccinamyldisodium, alkylamidepolyethoxy
sulfonylsuccinic acid disodium, disodium ethoxylated nonylphenol
sulfonylsuccinate, and sodium ethoxyethyl sulfate.
[0052] Specifically, the initiator may be hydrogen peroxide,
tert-butyl peroxides and alkali metal persulfates, such as sodium
persulfate, potassium persulfate, lithium persulfate and ammonium
persulfate (APS).
[0053] More specifically, the reducing agent may be sulfites such
as alkali metal metabisulfites, hydrogen sulfites and
hydrosulfites, sodium formaldehyde sulfoxylate (SFS), tert-butyl
hydroperoxide (TBHP), and reducing sugars such as ascorbic acid and
erythorbic acid. At a subsequent stage of emulsion polymerization,
in order to avoid the emulsion condensation caused by heating, the
reducing agent can be used at 50 to 70.degree. C. to post-eliminate
the monomers to reduce the monomer residual rate.
[0054] The present disclosure is further illustrated by the
following embodiments and comparative embodiment, but the scope of
the present disclosure is not limited to such examples.
Embodiment 1
[0055] A polyester polyol is synthesized from tricyclodecane
dimethanol (TCD-alcohol) and adipic acid (AA). 78.8 g of PTMG2000
(polyether diol having a molecular weight of 2000) and 6.44 g of
1,4-BG (1,4-butylene glycol having a molecular weight of 90) and 20
g of the aforementioned polyester polyol are mixed into a reactor,
and the mixture is heated to 80.degree. C. while stirring at
uniform speed. Afterwards, 51.3 g of 4,4'-diisocyanato
dicyclohexylmethane (H.sub.12MDI) is added and the temperature is
raised to 85 to 90.degree. C. for reaction for 2 to 3 hours.
Subsequently, 147.2 g of methyl methacrylate (MMA), 8 g of
2-hydroxyethyl acrylate (2-HEA), 4.8 g of ethyl acrylate (EA) are
added in order. Afterwards, 26.4 g of sodium ethylenediamino
sulfonate (AAS) is added to the prepolymer to continue the reaction
for 25 to 40 minutes. After cooling to room temperature, 472.6 g of
deionized water is added under a rotational speed of 500 rpm and
1.9 g of ethylenediamine is added for chain extension for 30
minutes, so as to obtain a water-based polyurethane.
[0056] 4.8 g of sodium lauryl sulfate (SLS) is added to the
aforesaid water-based polyurethane under high-speed stirring. The
resulting mixture is heated to 50 to 70.degree. C. and 0.40 g of
ammonium persulfate aqueous solution (APS) is then dropwise added.
The reaction temperature is raised to 75 to 85.degree. C. and
maintained thereat for 1 to 3 hours. After cooling to 50 to
70.degree. C., 0.15 g of tert-butyl hydroperoxide aqueous solution
(TBHP) and 0.16 g of sodium formaldehyde sulfoxylate (SFS) serving
as reducers are added for reaction for 30 minutes, so as to obtain
an acrylic-grafting-modified water-based polyurethane.
Embodiment 2
[0057] 98.8 g of PTMG2000 (polyether diol, molecular weight 2000)
and 6.44 g of 1,4-BG (1,4-butylene glycol, molecular weight 90) are
mixed into a reactor, and the mixture is heated to 80.degree. C.
while stirring at uniform speed. After that, 43.5 g of isophorone
diisocyanate (IPDI) is added and the temperature is raised to 85 to
90.degree. C. for reaction for 2-3 hours. Subsequently, 127.2 g of
methyl methacrylate (MMA), 8 g of 2-hydroxyethyl acrylate (2-HEA),
4.8 g of ethyl acrylate (EA), 16.8 g of cyclohexyl methacrylate
(CHMA) and 22.2 g of isobornyl methacrylate (IBOMA) are added in
order. After that, 26.4 g of sodium ethylenediamino sulfonate (AAS)
is added to the prepolymer to continue the reaction for 25 to 40
minutes. After cooling to room temperature, 472.6 g of deionized
water is added under a rotary speed of 500 rpm and 1.9 g of
ethylenediamine is added for chain extension for 30 minutes, so as
to obtain a water-based polyurethane.
[0058] 4.8 g of sodium lauryl sulfate (SLS) is added to the
aforesaid water-based polyurethane under high-speed stirring. The
resulting mixture is heated to 50 to 70.degree. C. and subsequently
0.40 g of ammonium persulfate aqueous solution (APS) is dropwise
added. The temperature is raised to 75 to 85.degree. C. and
maintained thereat for 1 to 3 hours. After cooling to 50 to
70.degree. C., 0.15 g of tert-butyl hydroperoxide aqueous solution
(TBHP) and 0.16 g of sodium formaldehyde sulfoxylate (SFS) serving
as reducers are added for reaction for 30 minutes, so as to obtain
an acrylic-grafting-modified water-based polyurethane.
Embodiment 3
[0059] A polyester polyol is synthesized from tricyclodecane
dimethanol (TCD-alcohol) and adipic acid (AA). 78.8 g of PTMG2000
(polyether diol, molecular weight 2000) and 6.44 g of 1,4-BG
(1,4-butylene glycol, molecular weight 90) and 20 g of the
aforementioned polyester polyol are mixed into a reactor, and the
mixture is heated to 80.degree. C. while stirring at uniform speed.
After that, 51.3 g of 4,4'-diisocyanato dicyclohexylmethane
(H.sub.12MDI) is added and the temperature is raised to 85 to
90.degree. C. for reaction for 2 to 3 hours. Subsequently, 127.2 g
of methyl methacrylate (MMA), 8 g of 2-hydroxyethyl acrylate
(2-HEA), 4.8 g of ethyl acrylate (EA), 16.8 g of cyclohexyl
methacrylate (CHMA) and 22.2 g of isobornyl methacrylate (IBOMA)
are added in order. After that, 26.4 g of sodium ethylenediamino
sulfonate (AAS) is added to the prepolymer to continue the reaction
for 25 to 40 minutes. After cooling to room temperature, 472.6 g of
deionized water is added under a rotary speed of 500 rpm and 1.9 g
of ethylenediamine is added for chain extension for 30 minutes, so
as to obtain a water-based polyurethane.
[0060] 4.8 g of sodium lauryl sulfate (SLS) is added to the
aforesaid water-based polyurethane under high-speed stirring. The
resulting mixture is heated to 50 to 70.degree. C. and subsequently
0.40 g of ammonium persulfate aqueous solution (APS) is dropwise
added. The temperature is raised to 75 to 85.degree. C. and
maintained thereat for 1 to 3 hours. After cooling to 50 to
70.degree. C., 0.15 g of tert-butyl hydroperoxide aqueous solution
(TBHP) and 0.16 g of sodium formaldehyde sulfoxylate (SFS) serving
as reducers are added for reaction for 30 minutes, so as to obtain
an acrylic-grafting-modified water-based polyurethane.
Comparative Embodiment 1
[0061] 98.8 g of PTMG2000 (polyether diol, molecular weight 2000)
and 6.44 g of 1,4-BG (1,4-butylene glycol, molecular weight 90) are
mixed into a reactor, and the mixture is heated to 80.degree. C.
while stirring at uniform speed. After that, 43.5 g of isophorone
diisocyanate (IPDI) is added and the temperature is raised to 85 to
90.degree. C. for reaction for 2 to 3 hours. Subsequently, 147.2 g
of methyl methacrylate (MMA), 8 g of 2-hydroxyethyl acrylate
(2-HEA), 4.8 g of ethyl acrylate (EA) are added in order for
dilution and reduction of viscosity of the resulting prepolymer.
After that, 26.4 g of sodium ethylenediamino sulfonate (AAS) is
added to the prepolymer to continue the reaction for 25 to 40
minutes. After cooling to room temperature, 472.6 g of deionized
water is added under a rotary speed of 500 rpm and 1.9 g of
ethylenediamine is added for chain extension for 30 minutes, so as
to obtain a water-based polyurethane.
[0062] 4.8 g of sodium lauryl sulfate (SLS) is added to the
aforesaid water-based polyurethane under high-speed stirring. The
resulting mixture is heated to 50 to 70.degree. C. and subsequently
0.40 g of ammonium persulfate aqueous solution (APS) is dropwise
added. The temperature is raised to 75 to 85.degree. C. and
maintained thereat for 1 to 3 hours. After cooling to 50 to
70.degree. C., 0.15 g of tert-butyl hydroperoxide aqueous solution
(TBHP) and 0.16 g of sodium formaldehyde sulfoxylate (SFS) serving
as reducers are added for reaction for 30 minutes, so as to obtain
an acrylic-grafting-modified water-based polyurethane.
[0063] The compositions of Embodiment 1 to 3 and Comparative
Embodiment 1 are respectively shown in Table 1. Further, the
water-based polyurethane resins thereof are respectively applied to
synthetic leathers for evaluation tests on physical properties. The
results are shown in Table 2.
TABLE-US-00001 TABLE 1 Comparative Compositions Embodiment 1
Embodiment 2 Embodiment 3 Embodiment 1 Polyol PTMG2000 78.8 g 98.8
g 78.8 g 98.8 g 1,4-BG 6.44 g 6.44 g 6.44 g 6.44 g A polyester 20 g
-- 20 g -- polyol synthesized from tricyclodecane dimethanol (TCD-
alcohol) and adipic acid (AA) Isocyanate H.sub.12MDI 51.3 g -- 51.3
g -- IPDI -- 43.5 g -- 43.5 g Acrylic CHMA -- 16.8 g 16.8 g --
monomer IBOMA -- 22.2 g 22.2 g -- MMA 147.2 g 127.2 g 127.2 g 147.2
g EA 4.8 g 4.8 g 4.8 g 4.8 g 2-HEA 8 g 8 g 8 g 8 g
TABLE-US-00002 TABLE 2 Comparative Result Embodiment 1 Embodiment 2
Embodiment 3 Embodiment 1 Crumpling No damage No damage No damage
No damage resistance (1.5 kg .times. 1000 times) Corner whitening
No No No No (3 kg .times. 24 hours) whitening whitening whitening
whitening Heat-resistant No sticking No sticking No sticking No
sticking adhesion (70.degree. C.*3 kg .times. 24 hours) Hydrolysis
No cracks No cracks No cracks No cracks resistance (10% NaOH
.times. 8 hours) Heat yellowing 4.1 4.0 3.8 4.5 resistance
120.degree. C. .times. 7 days .DELTA.E (smaller .DELTA.E value
indicates better yellowing resistance) Alcohol Slight Slight No
Bleaching resistance 1 kg .times. bleaching bleaching bleaching 10
times Weather Normal for Normal for Normal for Normal for
resistance 15 weeks 15 weeks 16 weeks 14 weeks (70.degree. C.
.times. 95% RH)
Beneficial Effects of the Embodiments
[0064] In conclusion, by virtue of "at least one of the polyol, the
polyisocyanate and the acrylic monomer includes a cyclic structure
compound", the thermal stability of the resin in the present
disclosure is improved.
[0065] In detail, when the conventional water-based polyurethane is
applied in synthetic leather material or surface treatment agent
field, the heat yellowing resistance and weathering resistance are
affected by the high temperature condition (120.degree. C..times.7
days). In general, additives such as light stabilizers,
antioxidants and heat stabilizers are applied to achieve the
purpose of improving the yellowing problem. However, the
improvement is still not very satisfactory.
[0066] Specifically, polyester polyols can also be polycyclohexane
dimethyl ester polymerized by 1,4 cyclohexane dimethanol and
dibasic acid, or polytricyclodecane dimethyl ester polymerized by
tricyclodecane dimethanol (TCD-alcohol) and dibasic acid.
Preferably, the diisocyanate is isophorone diisocyanate (IPDI) or
4,4'-diisocyanato dicyclohexylmethane (H.sub.12MDI).
[0067] More specifically, the acrylic monomer is a combination of
2-hydroxyethyl acrylate (2-HEA), methyl methacrylate (MMA) and
ethyl acrylate (EA), and is further combined with compounds with
cyclic structures such as cyclohexyl methacrylate (CHMA) and
isobornyl methacrylate (IBOMA). The structures of these compounds
all contain cyclic structures.
[0068] The polyol, the polyisocyanate and the acrylic monomers of
the present disclosure introduced cyclic structures into the
compound structure, which changes the segment structure, and
enhances the intermolecular force to improve and raise the thermal
stability of the water-based polyurethane resin. Therefore, the
water-based polyurethane resin of the present disclosure can be
applied to PVC rubber and PU synthetic leather treatment agent, and
can achieve a property of lower .DELTA.E (120.degree. C..times.7
days) heat yellowing resistance.
[0069] The foregoing description of the exemplary embodiments of
the disclosure has been presented only for the purposes of
illustration and description and is not intended to be exhaustive
or to limit the disclosure to the precise forms disclosed. Many
modifications and variations are possible in light of the above
teaching.
[0070] The embodiments were chosen and described in order to
explain the principles of the disclosure and their practical
application so as to enable others skilled in the art to utilize
the disclosure and various embodiments and with various
modifications as are suited to the particular use contemplated.
Alternative embodiments will become apparent to those skilled in
the art to which the present disclosure pertains without departing
from its spirit and scope.
* * * * *